KR20160100260A - Bisaminoalkoxysilane compounds and methods for using same to deposit silicon-containing films - Google Patents

Abstract

Disclosed is bisaminoalkoxysilane which is thermally stable and is represented by chemical formula 1, R^1Si(NR^2R^3)(NR^4R^5)OR^6. Also, disclosed is an application method thereof.

Description

FIELD OF THE INVENTION The present invention relates to bisaminoalkoxysilane compounds and their use in the deposition of silicon-containing films. BACKGROUND OF THE INVENTION < RTI ID = 0.0 > BISAMINOALKOXYSILANE COMPOUNDS AND METHODS FOR USING SAME TO DEPOSIT SILICON- CONTAINING FILMS &

Cross-reference to related application

This application claims priority from U.S. Provisional Application No. 62 / 115,729, filed February 13, 2015. The contents of this application are incorporated herein by reference in their entirety.

The present application discloses a process for preparing a film comprising a volatile and thermally stable aminoalkoxysilane, more particularly a bisaminoalkoxysilane, and a stoichiometric or non stoichiometric silicon-containing film such as, but not limited to, silicon oxide, silicon nitride, silicon oxynitride, Carbamide, and methods for use in depositing silicon oxycarbonitride films are described.

U.S. Pat. No. 4,491,669 discloses compounds of the general formula: R _m Si (OR ') _n (NR "R'") _p wherein R is hydrogen, short chain alkyl or alkenyl or aryl; '' Are independently hydrogen, short chain alkyl or aryl, at least one is not hydrogen, R 'is short chain alkyl or aryl, m, n and p are m + n + p = 4, Lt; RTI ID = 0.0 > 1, < / RTI > The resulting compound is used for end-capping the polysiloxane having a terminal silane group.

U.S. Pat. No. 4,345,088 describes compounds having the formula (R) ₂ NXSiHOR wherein X is OR or N (R) ₂ and R is alkyl of 1 to 8 carbon atoms. These compounds are prepared by treating a tris (dialkylamino) hydridosilane with an alkanol.

- 75

의 온도 범위에서 수행될 수 있고, 비양성자성 용매는 공정에서 재사용하기 위해 회수된다. 이에 따라, THF 중에서의 이소프로필마그네슘 클로라이드와 3차-부틸아민의 반응 이후 메틸트리메톡시실란로의 처리는 82%의 메틸(3차-부틸아미노)디메톡시실란을 제공하였다.U.S. Patent No. 6,114,558 discloses a general formula ^{RSi (NR 1 R 2) (} OR 3) 2 ( wherein, R is a 1 to a 20 linear or branched alkyl, arylalkyl or aryl radical of the carbon atom, R ¹ and R ² Is an alkyl radical of one to six carbon atoms, one of which may be hydrogen, and R < ³ > is an alkyl radical of 1-6 carbon atoms, with methyl being preferred) of an alkyl (amino) dialkoxysilane It describes the recipe. Alkyl (amino) dialkoxysilanes are prepared by reacting stoichiometric amounts of alkoxysilane and alkylamino magnesium chloride anhydrous in a reverse addition process. The alkylamino magnesium chloride is preferably prepared in situ by reaction of Grignard reagent (RMX) and alkylamine in a suitable aprotic solvent such as tetrahydrofuran (THF) . This reaction was carried out without catalyst

- 75

, And the aprotic solvent is recovered for re-use in the process. Accordingly, the treatment with methyltrimethoxysilane after the reaction of tertiary-butylamine with isopropylmagnesium chloride in THF provided 82% of methyl (tert-butylamino) dimethoxysilane.

U.S. Patent No. 7,524,735 describes a method involving filling a gap on a substrate with a solid dielectric material by forming a flowable film in the gap. The flowable film provides consistent, pore-free gap filling. The film is then converted to a solid dielectric material. In this way, the gaps on the substrate are filled with solid dielectric material. According to various embodiments, the method comprises reacting the dielectric precursor with an oxidizing agent to form a dielectric material. In certain embodiments, the dielectric precursor is condensed and then reacted with the oxidizing agent to form a dielectric material. In certain embodiments, the gaseous reactants react to form a condensed flowable film.

U.S. Patent No. 7,943,531 describes a method of depositing a silicon oxide layer on a substrate in a deposition chamber. A first silicon-containing precursor, a second silicon-containing precursor and an NH ₃ plasma react to form a silicon oxide layer. The first silicon-containing precursor comprises at least one of a Si-H bond and a Si-Si bond. The second silicon-containing precursor comprises at least one Si-N bond.

U.S. Patent No. 7,425,350 describes a method for producing a Si-containing material comprising transferring a pyrolyzed Si-precursor to a substrate and polymerizing the pyrolyzed Si-precursor on the substrate to form a Si-containing film. The polymerization of the pyrolyzed Si-precursor can be carried out in the presence of a porogen to form a porogen-containing Si-containing film. The porogen can be removed from the porogen-containing, Si-containing film to form a porous Si-containing film. Preferred porous Si-containing films have low dielectric constants and are therefore suitable for a variety of low-k applications such as in microelectronics and microelectromechanical systems.

U.S. Patent No. 7,888,273 describes a method of lining and / or filling a gap on a substrate by forming a flowable silicon oxide-containing film. The method includes introducing the vapor-phase silicon-containing precursor and the oxidant reactant into a reaction chamber containing the substrate under conditions that allow the condensed flowable film to be formed on the substrate. The flowable film at least partially fills the gap on the substrate and is then converted to a silicon oxide film. In certain embodiments, the method includes using a catalyst, such as a nucleophile or an onium catalyst, in film formation. The catalyst may be incorporated into one of the reactants and / or introduced as a separate reactant. Also provided is a method of converting a flowable film into a solid dielectric film. The method of the present invention can be used to lining or fill high aspect ratio gaps, including gaps having an aspect ratio in the range of 3: 1 to 10: 1.

U.S. Patent No. 7,629,227 describes a method of lining and / or filling a gap on a substrate by forming a flowable silicon oxide-containing film. The method includes introducing the vapor-phase silicon-containing precursor and the oxidant reactant into a reaction chamber containing the substrate under conditions that allow the condensed flowable film to be formed on the substrate. The flowable film is at least partially filled with a gap on the substrate, and then converted into a silicon oxide film. In certain embodiments, the method includes using a catalyst, such as a nucleophile or an onium catalyst, in film formation. The catalyst may be incorporated into one of the reactants and / or introduced as a separate reactant. Also provided is a method of converting a flowable film into a solid dielectric film. The method of the present invention can be used to lining or fill gaps having a high aspect ratio, including gaps having an aspect ratio ranging from 3: 1 to 10: 1.

WO 06129773 is (A) a solid catalyst component containing titanium, magnesium and halogen an electron donor compound, (B) the general formula R ⁶ _p AlQ organo aluminum compound represented by the _{3 -p} and (C) the general formula R ³ _n Si (NR ⁴ A catalyst for the polymerization of an olefin formed from an aminosilane compound represented by R < ⁵ >) _{4- n} ; And processes for producing catalysts for polymerizing olefins in the presence of catalysts.

또는 그 미만); 분당 약 0.1 나노미터 (nm) 내지 1000nm 범위의 비교적 우수한 증착 속도; 푸리에(Fourier) FTIR 또는 XPS에 의해 분석되는, 웨이퍼 상의 다수의 지점에 걸쳐 측정된

10% 이하의 편차를 갖는 조성 균일성; 높은 안정성(예를 들어, 1년에 약 5% 또는 그 미만 또는 1년에 약 1% 또는 그 미만의 분해율 진행); 전사 주사 현미경(scanning electron microcopy) (SEM)에 의해 관찰되는, 트렌치, 갭 또는 비아를 채우기 위한 유동성; 및 이들의 조합.Accordingly, there is a need in the prior art to provide precursors that can be used to deposit silicon-containing films that provide one or more of the following advantages: low processing temperatures (e.g., 500

Or less); A relatively good deposition rate in the range of about 0.1 nanometers (nm) to 1000 nm per minute; Measured over multiple points on the wafer, as analyzed by Fourier FTIR or XPS

Compositional uniformity with a deviation of 10% or less; High stability (e.g., a degradation rate of about 5% or less per year, or about 1% or less per year); Flowability for filling trenches, gaps or vias, as observed by scanning electron microcopy (SEM); And combinations thereof.

SUMMARY OF THE INVENTION

The present application discloses a bisaminoalkoxysilane precursor and precursors thereof on a substrate or on at least one surface of the substrate in a stoichiometric or non stoichiometric silicon-containing film such as, but not limited to, silicon oxide, silicon carbide, silicon nitride, Oxynitride, silicon carbide, silicon carbonitride, and combinations thereof. Also described herein is a method of forming a silicon-containing film or coating on a subject to be treated, for example, a semiconductor wafer.

In one aspect, there is provided a composition for depositing a silicon-containing film comprising at least one bisaminoalkoxysilane having the formula (I)

R ¹ Si (NR ² R ³ ) (NR ⁴ R ⁵ ) OR ⁶ (I)

In this formula,

R ¹ is a hydrogen atom, C ₁ to C ₁₀ linear alkyl, C ₃ to C ₁₀ branched alkyl, C ₃ to C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ alkenyl groups, C ₃ to C ₁₀ alkynyl group, C ₄ to is selected from C ₁₀ aromatic hydrocarbon group; Each of R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom, a C ₄ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ An alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; R ⁶ is a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₂ to C ₁₀ alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; Optionally in formula (I), R ² and R ³ , R ⁴ and R ⁵ , or both, may be joined together to form a ring; Optionally, in formula (I), R ² and R ⁴ may be bonded together to form a diamino group. Exemplary bisaminoalkoxysilane precursor compounds having formula (I) include bis (tert-butylamino) methoxymethylsilane, bis (tert-butylamino) ethoxymethylsilane, bis (cis-2,6-dimethyl Piperidino) methoxymethylsilane, and bis (cis-2,6-dimethylpiperidino) ethoxymethylsilane.

In yet another aspect, a method of forming a silicon-containing film on at least one surface of a substrate,

Providing a substrate to the reactor;

There is provided a method comprising forming a silicon-containing film on at least one surface by a deposition process using at least one precursor comprising a bisaminoalkoxysilane having the formula (I)

R ¹ Si (NR ² R ³ ) (NR ⁴ R ⁵ ) OR ⁶ (I)

In this formula,

R ¹ is a hydrogen atom, C ₁ to C ₁₀ linear alkyl, C ₃ to C ₁₀ branched alkyl, C ₃ to C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ alkenyl groups, C ₃ to C ₁₀ alkynyl group, C ₄ to is selected from C ₁₀ aromatic hydrocarbon group; Each of R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom, a C ₄ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ An alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; R ⁶ is a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₂ to C ₁₀ alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; Optionally in formula (I), R ² and R ³ , R ⁴ and R ⁵ , or both, may be joined together to form a ring; Optionally, in formula (I), R ² and R ⁴ may be bonded together to form a diamino group.

In another aspect, a method of forming a silicon oxide or carbon doped silicon oxide film through an atomic layer deposition process or a cyclic chemical vapor deposition process,

a. Providing a substrate to the reactor;

b. Introducing at least one precursor comprising a bisaminoalkoxysilane compound having the following formula (I) in a reactor:

R ¹ Si (NR ² R ³ ) (NR ⁴ R ⁵ ) OR ⁶ (I)

Wherein R ¹ is a hydrogen atom, a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ alkynyl group, A C ₄ to C ₁₀ aromatic hydrocarbon group; Each of R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom, a C ₄ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ An alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; R ⁶ is a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₂ to C ₁₀ alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; Optionally in formula (I), R ² and R ³ , R ⁴ and R ⁵ , or both, may be joined together to form a ring; Optionally R < ² > and R < ⁴ > in the formula (I) may be joined together to form a diamino group;

c. Purging the reactor with a purge gas;

d. Introducing an oxygen source into the reactor; And

e. Purging the reactor with a purge gas;

Steps b to e are repeated until a film of the desired thickness is obtained.

In a further aspect, a method of forming a silicon oxide or carbon-doped silicon oxide film on at least one surface of a substrate using a CVD process,

a. Providing a substrate to the reactor;

b. Introducing at least one precursor comprising a bisaminoalkoxysilane compound having the following formula (I) in a reactor:

R ¹ Si (NR ² R ³ ) (NR ⁴ R ⁵ ) OR ⁶ (I)

Wherein R ¹ is a hydrogen atom, a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ alkynyl group, A C ₄ to C ₁₀ aromatic hydrocarbon group; Each of R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom, a C ₄ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ An alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; R ⁶ is a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₂ to C ₁₀ alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; Optionally in formula (I), R ² and R ³ , R ⁴ and R ⁵ , or both, may be joined together to form a ring; Optionally R < ² > and R < ⁴ > in the formula (I) may be joined together to form a diamino group; And

c. And providing an oxygen source to deposit a silicon oxide or carbon doped silicon oxide film on at least one surface.

In another embodiment, a method of forming a silicon nitride or silicon oxynitride or silicon carboxynitride film through an atomic layer deposition process or a cyclic chemical vapor deposition process,

a. Providing a substrate to the reactor;

b. Introducing at least one precursor comprising a bisaminoalkoxysilane compound having the following formula (I) in a reactor:

R ¹ Si (NR ² R ³ ) (NR ⁴ R ⁵ ) OR ⁶ (I)

Wherein R ¹ is a hydrogen atom, a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ alkynyl group, A C ₄ to C ₁₀ aromatic hydrocarbon group; Each of R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom, a C ₄ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ An alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; R ⁶ is a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₂ to C ₁₀ alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; Optionally in formula (I), R ² and R ³ , R ⁴ and R ⁵ , or both, may be joined together to form a ring; Optionally R < ² > and R < ⁴ > in the formula (I) may be joined together to form a diamino group;

c. Purging the reactor with a purge gas;

d. Feeding a nitrogen-containing source to the reactor; And

e. Purging the reactor with a purge gas;

Steps b to e are repeated until a silicon nitride or silicon oxynitride or silicon carboxynitride film of the desired thickness is obtained.

In a further aspect, a method of forming a silicon nitride or silicon oxynitride film on at least one surface of a substrate using a CVD process,

a. Providing a substrate to the reactor;

b. Introducing into the reactor at least one precursor comprising a bisaminoalkoxysilane compound having the formula (I)

R ¹ Si (NR ² R ³ ) (NR ⁴ R ⁵ ) OR ⁶ (I)

Wherein R ¹ is a hydrogen atom, a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ alkynyl group, A C ₄ to C ₁₀ aromatic hydrocarbon group; Each of R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom, a C ₄ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ An alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; R ⁶ is a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₂ to C ₁₀ alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; Optionally in formula (I), R ² and R ³ , R ⁴ and R ⁵ , or both, may be joined together to form a ring; Optionally R < ² > and R < ⁴ > in the formula (I) may be joined together to form a diamino group;

c. There is provided a method comprising providing a nitrogen-containing source, wherein at least one bisaminoalkoxysilane precursor and a nitrogen-containing source are reacted to deposit a film comprising both silicon and nitrogen on at least one surface.

In another embodiment, a vessel for depositing a silicon-containing film comprising at least one bisaminoalkoxysilane precursor compound having the formula (I) is described herein. In one particular embodiment, the vessel comprises at least one pressurizable vessel (preferably made of stainless steel) equipped with suitable valves and fittings to deliver one or more precursors to the reactor for CVD or ALD processes do.

In another aspect, there is provided a composition for depositing a silicon-containing film comprising at least one precursor comprising a bisaminoalkoxysilane compound having the formula (I)

R ¹ Si (NR ² R ³ ) (NR ⁴ R ⁵ ) OR ⁶ (I)

In this formula,

R ¹ is a hydrogen atom, C ₁ to C ₁₀ linear alkyl, C ₃ to C ₁₀ branched alkyl, C ₃ to C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ alkenyl groups, C ₃ to C ₁₀ alkynyl group, C ₄ to is selected from C ₁₀ aromatic hydrocarbon group; Each of R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom, a C ₄ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ An alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; R ⁶ is a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₂ to C ₁₀ alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; Optionally in formula (I), R ² and R ³ , R ⁴ and R ⁵ , or both, may be joined together to form a ring; Optionally, in formula (I), R ² and R ⁴ may be bonded together to form a diamino group.

DETAILED DESCRIPTION OF THE INVENTION

The bisaminoalkoxysilane compounds can be deposited using a variety of deposition processes to deposit stoichiometric and non-stoichiometric silicon-containing films, such as, but not limited to, silicon oxide, silicon oxycarbide, silicon nitride, silicon oxynitride and silicon oxycarbonitride As a precursor. The bisaminoalkoxysilane precursors described herein are volatile liquid precursors of high purity (for example, from about 90% to about 99.9 or from about 95% to 99% of the assay results, as measured by gas chromatography (GC)) .

The precursors are typically vaporized and transferred to the deposition chamber or reactor as a gas for chemical vapor deposition (CVD), cyclic chemical vapor deposition (CCVD), plasma enhanced chemical vapor deposition (PECVD), liquid chemical vapor deposition Containing film through various deposition techniques including, but not limited to, chemical vapor deposition (FCVD), atomic layer deposition (ALD), and plasma enhanced atomic layer deposition (PEALD). In other embodiments, the bisaminoalkoxysilane precursors can be used in a liquid-based deposition or film formation process, such as, but not limited to, spin-on, dip coat, aerosol, ink jet, screen printing, or spray application. The choice of precursor material for deposition is based on the dielectric material or film of the desired result. For example, the precursor material may be selected as a silicon-containing film or coating, the content of which is determined by its chemical element content, its stoichiometric ratio of chemical elements, and / or the deposition processes mentioned above. The precursor materials may also be selected with any of the following features: cost, non-toxicity, handling characteristics, ability to maintain liquid at room temperature, volatility, molecular weight and / or other considerations. In certain embodiments, the precursors described herein may be used in a reactor system, such as a pressurized vessel, using a pressurizable stainless steel vessel equipped with suitable valves and fittings to deliver the liquid precursor to the deposition chamber or reactor, Lt; / RTI >

또는 그 미만에서, 400

또는 그 미만에서, 또는 300

또는 그 미만에서 고밀도 물질을 증착시킬 수 있다. 그 밖의 구체예들에서, 본원에서 기술되는 전구체는 예를 들어, 약 500

내지 약 800 범위의 온도에서의 보다 고온 증착에 사용될 수 있다. The bisaminoalkoxysilane precursors described herein are characterized in that the precursors have at least one of the bonds Si-N, Si-O, optionally Si-H and optionally Si-NH, , It is believed that it can provide better reactivity to the substrate surface during chemical vapor deposition or atomic layer deposition. The bisaminoalkoxysilane precursors described herein provide a better reactivity to the substrate surface during chemical vapor deposition, especially cyclic CVD deposition, or ALD, such that Si-N-Si connections or Si-O-Si connections Can be formed. In certain embodiments, such as those for depositing silicon oxide or silicon nitride films using cyclic CVD, ALD, or PEALD deposition methods, in addition to the above advantages, the bisaminoalkoxysilane precursors described herein are relatively low At the deposition temperature, for example, 500

Or below, 400

Or less, or 300

Or less. ≪ / RTI > In other embodiments, the precursors described herein include, for example, about 500

To about 800 Lt; RTI ID = 0.0 > temperature. ≪ / RTI >

Without being bound by theory, it is believed that the compounds described herein overcome the problems associated with other precursors in the prior art by having substituents or ligands whose relative reactivity varies. In this regard, the compounds are highly reactive and contain silicon-amine substituents that tend to react with protic reagents, such as, but not limited to, water in a fast manner. This feature allows the precursors to rapidly deposit the flowable film under capillary co-condensation conditions between the precursor, the protic reagent, and any cosolvent. In order to prevent rapid reaction from causing premature solidification, the number of highly reactive substituents can be limited to no more than two per silicon atom, which is a fast three-dimensional networked polymer, Means that the remaining slower reactive substituents can not be formed until they are reacted. An example of this is a compound of formula (I) wherein R ¹ = methyl (Me), R ² = R ⁴ = hydrogen, R ³ = R ⁵ = tert-butyl, R ⁶ = Me, 1000, and m = an integer from 4 to 1,000. Scheme A shows that the tertiary-butylamino substituent reacts rapidly or within seconds of contact with water, while the methyl hydroxyl substituent is relatively slow compared to the tertiary-butylamino substituent, ranging from a few minutes to several hours Lt; / RTI >

Scheme A

In one embodiment, a deposition process using a bisaminoalkoxysilane compound having the following formula (I) is described herein:

R ¹ Si (NR ² R ³ ) (NR ⁴ R ⁵ ) OR ⁶ (I)

In this formula,

R ¹ is a hydrogen atom, C ₁ to C ₁₀ linear alkyl, C ₃ to C ₁₀ branched alkyl, C ₃ to C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ alkenyl groups, C ₃ to C ₁₀ alkynyl group, C ₄ to is selected from C ₁₀ aromatic hydrocarbon group; Each of R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom, a C ₄ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ An alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; R ⁶ is a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₂ to C ₁₀ alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; Optionally in formula (I), R ² and R ³ , R ⁴ and R ⁵ , or both, may be joined together to form a ring; Optionally, in formula (I), R ² and R ⁴ may be bonded together to form a diamino group.

In one particular embodiment of formula (I), R ² and R ⁴ are both hydrogen atoms and R ³ and R ⁵ are independently C ₄ to C ₁₀ branched alkyl groups such as tert-butyl or tert-pentyl Tyl group. Without being bound by any particular theory, it is believed that the steric hindrance of the branched alkyl group provides better thermal stability. As used herein, the term "stable" means that the precursors described herein are stable for a period of six (6) months or more, one (1) year or more, a period of (2) (Wt)% or more, 1 wt% or more, 2 wt% or more, 5 wt% or more, or 10 wt% or more in its initial composition after storage for a period of time . For example, the concentration of the precursor may be stored for one year to be considered stable as described herein, and then stored in a solution containing more than 10% of its initial proportion based on gas chromatography (GC) It should not change sexually. The excellent thermal and compositional stability of the precursor is important to ensure consistent precursor delivery to the vapor deposition chamber and consistent vapor deposition parameters. In addition, excellent thermal stability also reduces the exchangeability of substituents or ligands during storage and handling.

In the context of formula (I) and throughout the description, the term "linear alkyl" denotes a linear functional group having 1 to 10 or 1 to 4 carbon atoms. Exemplary linear alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, and hexyl groups. In the context of general formula (I) and throughout the description, the term "branched alkyl" denotes a branched functional group having 3 to 10 or 4 to 6 carbon atoms. Exemplary alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, iso-pentyl, tert-pentyl, and isohexyl. In certain embodiments, the alkyl group may have one or more functional groups attached thereto, such as, but not limited to, an alkoxy group, a dialkylamino group, or combinations thereof. In other embodiments, the alkyl group has no more than one functional group attached thereto.

In the context of formula (I) and throughout the description, the term "cyclic alkyl" refers to a cyclic functional group having 3 to 10 or 4 to 10 carbon atoms. Exemplary cyclic alkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

In the context of formula (I) and throughout the description, the term "aromatic hydrocarbon" denotes an aromatic cyclic functional group having from 4 to 10 carbon atoms. Exemplary aryl groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl, and o-xylyl. In certain embodiments, the aromatic hydrocarbon group has at least one functional group.

In the context of formula (I) and throughout the description, the term "alkenyl group" refers to a group having one or more carbon-carbon double bonds and having 3 to 10, or 2 to 6 carbon atoms. Exemplary alkenyl groups include, but are not limited to, vinyl or allyl groups.

In the context of formula (I) and throughout the description, the term "alkynyl group " refers to a group having one or more carbon-carbon triple bonds and having 3 to 10, or 2 to 6 carbon atoms.

In the context of formula (I) and throughout the description, the term "alkoxy" refers to an alkyl group having 1 to 12, or 1 to 6 carbon atoms, connected to an oxygen atom (eg, RO). Exemplary alkoxy groups are methoxy (-OCH _3), ethoxy (-OCH ₂ CH _3), n- propoxy _{(-OCH 2 CH 2 CH 3)} , and iso-propoxy, including, (-OCHMe _2), But is not limited thereto.

In certain embodiments, at least one of the alkyl group, alkenyl group, alkynyl group, alkoxy group, and / or aryl group in formula (I) is substituted or substituted by, for example, a group of one or more atoms or atoms ≪ / RTI > Exemplary substituents include, but are not limited to, oxygen, sulfur, halogen atoms (e.g., F, Cl, I, or Br), nitrogen, and phosphorus. In one particular embodiment, the alkyl group in formula (I) may comprise oxygen or nitrogen. In other embodiments, at least one of the alkyl group, alkenyl group, alkynyl group, alkoxy group, and / or aryl group in formula (I) may be unsubstituted.

Examples of bisaminoalkoxysilanes of formula (I) described herein include bis (tert-butylamino) methoxymethylsilane, bis (tert-butylamino) ethoxymethylsilane, bis (cis- Dimethylpiperidino) methoxymethylsilane, and bis (cis-2,6-dimethylpiperidino) ethoxymethylsilane.

In certain embodiments of the invention described herein, the bisaminoalkoxysilane precursor having the formula (I) is selected from the group consisting of dialkylaminosilanes, alkoxysilanes, dialkylaminoalkylsilanes, and alkoxyalkylsilanes. Lt; RTI ID = 0.0 > silicon-containing < / RTI > precursor to provide a composition for depositing a silicon-containing film. In these embodiments, the composition comprises a bisaminoalkoxysilane having the formula (I) and a silicon-containing precursor. Examples of silicon-containing precursors for these compositions are bis (tert-butylamino) silane (BTBAS), tris (dimethylamino) silane (TRDMAS), tetraethoxysilane (TEOS), triethoxysilane Di-tert-butoxysilane (DTBOS), di-tert-pentoxysilane (DTPOS), methyltriethoxysilane (MTES), tetramethoxysilane (TMOS), trimethoxysilane But are not limited to, trimethoxysilane (MTMOS), di-tert-butoxymethylsilane, di-tert-butoxyethylsilane, di-tert-pentoxymethylsilane, But is not limited to one.

Examples of compositions comprising a silicon-containing precursor and a bisaminoalkoxysilane of formula (I) include tetraethoxysilane (TEOS) and di-ethoxy (tert-butylamino) silane, tetraethoxysilane (TEOS) Triethoxysilane (TES) and diethoxy (tert-butylamino) silane, tetraethoxysilane (TEOS) and diethoxy (iso-propoxyamino) silane, triethoxysilane Ethoxy silane (TES) and diethoxy (tert-pentylamino) silane, triethoxysilane (TES) and diethoxy (iso-propoxyamino) silane, di- tert-butoxysilane (DTBOS) Butoxy silane (DTBOS), di-tert-butoxy silane (DTBOS), di-tert-butoxy Butoxy silane, di-tert-butoxy silane (DTBOS) and di-tert-butoxy (n-butylamino) silane, di-tert-butoxy silane DTBOS) and di-tert-butoxy (sec-butylamino) silane Butoxy silane (DTBOS) and di-tert-butoxy silane (DTBOS) and di-tert-butoxy silane (DTBOS) (DTPOS) and di-tert-pentoxy (methylamino) silane, di-tert-pentoxy silane (DTPOS) (Diethylamino) silane, di-tert-pentoxysilane (DTPOS) and di-tert-pentoxy (iso-propylamino) silane, di- (DTPOS) and di-tert-pentoxy (sec-butylamino) silane, di-tert-pentoxysilane (DTPOS) and But are not limited to, di-tert-pentoxy (iso-butylamino) silane, di-tert-pentoxysilane (DTPOS) and di-tert-pentoxy (tert-butylamino) . In one particular embodiment, the composition is used to deposit a silicon oxide film by flow chemical vapor deposition, wherein the bisaminoalkoxysilane having the formula (I) serves as a catalyst. In these or other embodiments, the silicon-containing precursor is selected to be compatible with the bisaminoalkoxysilane, for example, by having the same alkoxy substituent.

As previously mentioned, deposition processes used to form silicon-containing films or coatings are deposition processes. Examples of suitable deposition processes for the methods described herein include, but are not limited to, chemical vapor deposition processes such as chemical vapor deposition (CCVD), thermal chemical vapor deposition, plasma enhanced chemical vapor deposition (PECVD), high density PECVD, photon assisted CVD, But are not limited to, vapor deposition, chemical assisted vapor deposition, high temperature-filament chemical vapor deposition, CVD of liquid polymer precursors, and low energy chemical vapor deposition (LECVD), and fluid chemical vapor deposition (FCVD).

또는 그 미만, 50

또는 그 미만, 20

또는 그 미만, 심지어 0

또는 그 미만에서 인시츄 촉매로서의 오가노아민의 방출로 인해 촉매로서 본원에서 기술된 그러한 조성물과 같은 다른 실리콘-함유 전구체들과 조합하여 사용될 수 있다. In certain embodiments, such as for depositing silicon oxide using typical FCVD processes, the bisaminoalkoxysilane precursors described herein have relatively low deposition temperatures, such as 100 < RTI ID = 0.0 >

Or less, 50

Or less, 20

Or less, even 0

Containing precursors such as those described herein as catalysts due to the release of the organoamines as in situ catalysts in the presence or in the absence of a catalyst.

The term "chemical vapor deposition processes " as used herein refers to any process in which the substrate is exposed to one or more volatile precursors that react and / or decompose on the substrate surface, resulting in the desired deposition.

As used herein, the term "atomic layer deposition process" refers to a self-limiting (e.g., constant amount of film material deposited in each reaction cycle) continuous surface chemistry that deposits film material on a variable composition substrate . In one embodiment, the film is alternatively deposited via an ADL process by exposing the substrate surface to one or more silicon-containing precursors, an oxygen source, a nitrogen-containing source, or other precursor or reagent. Film growth proceeds by self-limiting control of surface reaction, pulse length of each precursor or reagent, and deposition temperature. However, when the surface of the substrate is saturated, the film growth stops.

Although the precursors, reagents and sources used herein may sometimes be described as "gaseous ", the precursor may be a liquid or solid that is passed to the reactor via direct vaporization, bubbling or sublimation with or without inert gas . In some cases, the vaporized precursor may pass through the plasma generator.

The term "reactor" as used herein includes, but is not limited to, a reaction chamber or a deposition chamber.

Based on the deposition method, the bisaminoalkoxysilane precursor having the formula (I) in certain embodiments, other silicon-containing precursors, may be introduced into the reactor at a pre-determined molar volume, or from about 0.1 to about 1000 micromoles. In these or other embodiments, the bisaminoalkoxysilane precursor may be introduced into the reactor for a predefined period of time. In certain embodiments, the duration ranges from about 0.001 to about 500 seconds.

In certain embodiments, the silicon-containing film deposited using the methods described herein is formed in the presence of oxygen using an oxygen source, reagent, or precursor comprising oxygen.

The oxygen source may be introduced into the reactor in the form of at least one oxygen source and / or may be inadvertently present in the remaining precursor used in the deposition process.

Suitable oxygen source gases include, for example, water (H ₂ O) (e.g., deionized water, purified water and / or distilled water, a mixture containing water and other organic liquids), oxygen (O ₂ ) (O ₃ ), NO, NO ₂ , carbon monoxide (CO), hydrogen peroxide, a composition comprising hydrogen and oxygen, carbon dioxide (CO ₂ ), and combinations thereof. The organic liquid in the mixture may be selected from hydrocarbons, aromatic hydrocarbons, ethers, amines, ketones, esters, alcohols, organic acids, diols, acetylenic alcohols and organic amides.

In certain embodiments, the oxygen source comprises an oxygen source gas introduced into the reactor at a flow rate ranging from about 1 to about 2000 square centimeters (sccm) or from about 1 to about 1000 sccm. The oxygen source may be introduced for a time ranging from about 0.1 to about 100 seconds.

또는 그 초과의 온도를 갖는 물을 포함한다. In one particular embodiment, the oxygen source is 10

Or higher. ≪ / RTI >

In embodiments where the film is deposited by an ALD or cyclic CVD process, the precursor pulse may have a pulse duration of greater than 0.01 seconds, the oxygen source may have a pulse width of less than 0.01 seconds, The width can have a pulse width less than 0.01 second.

In still another embodiment, the pulse width between pulses, which may be as low as zero second, is pulsed continuously without purge. The oxygen source or reagent is provided in a molecular weight of less than 1: 1 relative to the silicon precursor such that at least some of the carbon is retained in the deposited silicon-containing film.

In certain embodiments, the oxygen source is continuously introduced into the reactor while the precursor pulses and plasma are introduced sequentially. The precursor pulse may have a pulse width of greater than 0.01 seconds, and the plasma width may range from 0.01 to 100 seconds.

In certain embodiments, the silicon-containing film comprises silicon and nitrogen. In these embodiments, a silicon-containing film deposited using the methods described herein is formed in the presence of a nitrogen-containing source. The nitrogen-containing source may be introduced into the reactor in the form of one or more nitrogen sources and / or may be accidentally present in the remaining precursors used in the deposition process.

Suitable nitrogen-containing source gas, e.g., ammonia, hydrazine, monoalkyl hydrazine, symmetric or asymmetric dialkyl hydrazine, N, NO, N ₂ O, NO _2, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, ammonia / nitrogen Plasma, a nitrogen / hydrogen plasma, an organoamine plasma, and mixtures thereof. In embodiments in which the organoamine plasma is used as a nitrogen-containing source, exemplary organic amine plasma includes diethylamine plasma, dimethylamine plasma, trimethyl plasma, trimethylamine plasma, ethylenediamine plasma, and alkoxy amines such as ethanolamine But are not limited to, plasma.

In certain embodiments, the nitrogen-containing source comprises a plasma source gas or an ammonia plasma comprising hydrogen and nitrogen introduced into the reactor at a flow rate ranging from about 1 to about 2000 square centimeters (sccm) or from about 1 to about 1000 sccm .

The nitrogen-containing source may be introduced for a time ranging from about 0.1 to about 100 seconds. In embodiments in which the film is deposited by an ALD or cyclic CVD process, the precursor pulse may have a pulse width in excess of 0.01 seconds and the nitrogen-containing source may have a pulse width of less than 0.01 seconds, And may have a pulse width less than 0.01 second. In yet another embodiment, the pulse width between pulses, which may be as low as zero seconds, is pulsed continuously without purging.

The deposition methods described herein may include one or more purge gases. The purge gas used to purge unburned reactants and / or reaction by-products is an inert gas that has not reacted with the precursor. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N ₂ ), helium (He), neon, hydrogen (H ₂ ), and mixtures thereof. In certain embodiments, the purge gas, such as Ar, is pumped into the reactor in a flow rate range of from about 10 to about 2000 sccm for from about 0.1 to about 1000 seconds to purge unreacted materials and any byproducts that may remain in the reactor.

Each step of supplying a precursor, an oxygen source, a nitrogen-containing source, and / or other precursors, a source gas, and / or a reagent may vary the time of supplying them so that the stoichiometric composition of the formed film is changed. . ≪ / RTI >

Energy is applied to at least one of a precursor, a nitrogen-containing source, a reducing agent, another precursor, or a combination thereof to induce a reaction and form a film or coating on the substrate. These energies include, but are not limited to, thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-ray, e-beam, photon, remote plasma methods, And combinations thereof.

In certain embodiments, a secondary RF frequency source may be used to modify the plasma characteristics at the substrate surface. In embodiments where the deposition includes a plasma, the plasma-generating process may be a direct plasma-generating process in which the plasma is generated directly in the reactor, or alternatively a remote plasma-generating process in which the plasma is generated outside the reactor and fed to the reactor .

The bisaminoalkoxysilane precursor and / or other silicon-containing precursors may be delivered to the reaction chamber, such as a CVD or ALD reactor, in a number of ways. In one embodiment, a liquid delivery system can be used. In alternative embodiments, a combined liquid transfer and flash vaporization process unit, such as a turbo vaporizer manufactured by, for example, MSP Corporation (Shoreview, Minn.) May be used to volatilize the low volatility material Which leads to reproducible transport and deposition without pyrolysis of the precursor. In liquid delivery formulations, the precursors described herein can be delivered in the form of a pure liquid, or alternatively can be used in solvent formulations or compositions containing them. Thus, in certain embodiments, precursor formulations may include solvent component (s) of suitable characteristics as may be desirable and advantageous in the end use applications presented to form a film on a substrate.

In the above or other embodiments, the steps of the method described herein may be performed in various orders, and may be performed sequentially or simultaneously (e.g., during at least a portion of another step) It should be understood that the invention may be practiced in combination. Each step of supplying the precursor and the nitrogen-containing source gas may be performed by varying the stoichiometric composition of the silicon-containing film formed by varying the duration of feeding them.

In another embodiment of the method described herein, the silicon-containing film comprises

Providing a substrate to an ALD reactor;

Introducing at least one precursor comprising a bisaminoalkoxysilane compound having the following formula (I) in an ALD reactor:

R ¹ Si (NR ² R ³ ) (NR ⁴ R ⁵ ) OR ⁶ (I)

Wherein R ¹ is a hydrogen atom, a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ alkynyl group, A C ₄ to C ₁₀ aromatic hydrocarbon group; Each of R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom, a C ₄ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ An alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; R ⁶ is a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₂ to C ₁₀ alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; Optionally in formula (I), R ² and R ³ , R ⁴ and R ⁵ , or both, may be joined together to form a ring; Optionally R < ² > and R < ⁴ > in the formula (I) may be joined together to form a diamino group;

Chemisorbing at least one bisaminoalkoxysilane precursor onto a substrate;

Purging at least one unreacted bisaminoalkoxysilane precursor using a purge gas;

Providing a nitrogen-containing source to at least one bisaminoalkoxysilane precursor on a heated substrate to react with at least one adsorbed bisaminoalkoxysilane precursor; And

And optionally purging any unreacted nitrogen-containing source.

In another embodiment of the method described herein, the silicon-containing film comprises

Providing a substrate to the reactor;

Introducing at least one precursor comprising a bisaminoalkoxysilane compound having the following formula (I) in a reactor:

R ¹ Si (NR ² R ³ ) (NR ⁴ R ⁵ ) OR ⁶ (I)

Wherein R ¹ is a hydrogen atom, a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ alkynyl group, A C ₄ to C ₁₀ aromatic hydrocarbon group; Each of R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom, a C ₄ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ An alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; R ⁶ is a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₂ to C ₁₀ alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; Optionally in formula (I), R ² and R ³ , R ⁴ and R ⁵ , or both, may be joined together to form a ring; Optionally R < ² > and R < ⁴ > in the formula (I) may be joined together to form a diamino group;

Chemisorbing at least one bisaminoalkoxysilane precursor onto a substrate;

Purging at least one unreacted bisaminoalkoxysilane precursor using a purge gas;

Providing an oxygen source to at least one bisaminoalkoxysilane precursor on a heated substrate to react with at least one adsorbed bisaminoalkoxysilane precursor; And

Optionally purge any unreacted oxygen source. ≪ RTI ID = 0.0 >

The steps define one cycle for the method described herein; The cycle may be repeated until the desired thickness of the silicon-containing film is achieved. In the above or other embodiments, the steps of the method described herein may be performed in various orders, and may be performed sequentially or simultaneously (e.g., during at least a portion of another step) It should be understood that the invention may be practiced in combination. Each step of supplying the precursor and the oxygen source does not always use less than the stoichiometric amount of silicon for the available silicon, but it is also possible to vary the duration of supplying them so that the stoichiometric composition of the formed silicon- . In multi-component silicon-containing films, other precursors such as silicon-containing precursors, nitrogen-containing precursors, reducing agents, or other reagents can alternatively be introduced into the reactor chamber.

In further embodiments of the methods described herein, the silicon and oxide containing films are deposited using a thermal CVD process. In this embodiment,

범위의 온도로 가열되고, 10 Torr 또는 그 미만의 압력에서 유지되는 반응기에 배치하고; The at least one substrate is heated from ambient temperature to about 700 <

Lt; RTI ID = 0.0 > 10 Torr < / RTI > or less;

Introducing at least one precursor comprising a bisaminoalkoxysilane compound having the formula (I)

R ¹ Si (NR ² R ³ ) (NR ⁴ R ⁵ ) OR ⁶ (I)

Wherein R ¹ is a hydrogen atom, a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ alkynyl group, A C ₄ to C ₁₀ aromatic hydrocarbon group; Each of R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom, a C ₄ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ An alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; R ⁶ is a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₂ to C ₁₀ alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; Optionally in formula (I), R ² and R ³ , R ⁴ and R ⁵ , or both, may be joined together to form a ring; Optionally R < ² > and R < ⁴ > in the formula (I) may be joined together to form a diamino group;

Supplying an oxygen source to the reactor to at least partially react with the at least one bisaminoalkoxysilane precursor, and depositing the film on the at least one substrate. In certain embodiments of the CVD method, the reactor is maintained at a pressure in the range of 100 mTorr to 10 Torr during the introduction step.

The steps define one cycle for the method described herein; The cycle may be repeated until the desired thickness of the silicon-containing film is achieved. In the above or other embodiments, the steps of the method described herein may be performed in various orders, and may be performed sequentially or simultaneously (e.g., during at least a portion of another step) It should be understood that the invention may be practiced in combination. Each step of supplying the precursor and the oxygen source does not always use less than the stoichiometric amount of silicon for the available silicon, but it is also possible to vary the duration of supplying them so that the stoichiometric composition of the formed silicon- . In multi-component silicon-containing films, other precursors, such as silicon-containing precursors, nitrogen-containing precursors, oxygen sources, reducing agents, or other reagents, may alternatively be introduced into the reactor chamber.

In further embodiments of the methods described herein, the silicon and oxide containing films are deposited using a thermal CVD process. In this embodiment,

범위의 온도로 가열되고, 10 Torr 또는 그 미만의 압력에서 유지되는 반응기에 배치하고; The at least one substrate is heated from ambient temperature to about 700 <

Lt; RTI ID = 0.0 > 10 Torr < / RTI > or less;

Introducing at least one precursor comprising a bisaminoalkoxysilane compound having the formula (I)

R ¹ Si (NR ² R ³ ) (NR ⁴ R ⁵ ) OR ⁶ (I)

Wherein R ¹ is a hydrogen atom, a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ alkynyl group, A C ₄ to C ₁₀ aromatic hydrocarbon group; Each of R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom, a C ₄ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ An alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; R ⁶ is a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₂ to C ₁₀ alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; Optionally in formula (I), R ² and R ³ , R ⁴ and R ⁵ , or both, may be joined together to form a ring; Optionally R < ² > and R < ⁴ > in the formula (I) may be joined together to form a diamino group; And

Providing a reactor with a nitrogen-containing source to at least partially react with at least one bisaminoalkoxysilane precursor, and depositing a silicon-containing film onto the at least one substrate. In certain embodiments of the CVD method, the reactor is maintained at a pressure in the range of 100 mTorr to 10 Torr during the introduction step.

As noted above, the processes described herein may be combined with additional precursors, such as, for example, bis-aminoalkoxysilane compounds having formula (I) in combination with another silicon-containing precursor such as those described herein, Can be used to deposit films. In these embodiments, the at least one precursor is described as a first precursor, a second precursor, a third precursor, etc. based on the number of different precursors used. The process can be used, for example, for cyclic chemical vapor deposition or atomic layer deposition. In these or other embodiments, the precursor may be introduced in a variety of ways (e.g., a. Introducing a first precursor; b. Purging; c. Introducing a second precursor; d. Fusing, etc., or alternatively, a) introduction of a first precursor, b) purging, c. Introduction of a second precursor, d) purging, e. In one particular embodiment,

a. Contacting the vapor generated from the first precursor with the heated substrate to chemically adsorb the first precursor on the heated substrate;

b. Purging any unadsorbed precursor;

c. Introducing an oxygen source onto the heated substrate to react with the adsorbed first precursor;

d. Purging any unreacted oxygen source;

e. Contacting the heated precursor with a vapor generated from a second precursor different from the first precursor to chemically adsorb a second precursor on the heated substrate;

f. purging any unadsorbed precursor;

g. Introducing an oxygen source onto the heated substrate to react with the adsorbed first and second precursors; And

h. Purging any unadsorbed oxygen source;

Steps a to h provide a process for depositing a silicon-containing film that repeats until a desired thickness is reached.

In still another embodiment of the process described herein,

a. Contacting the vapor generated from the first precursor with the heated substrate to chemically adsorb the first precursor on the heated substrate;

b. Purging any unadsorbed first precursor;

c. Introducing a nitrogen source onto the heated substrate to react with the adsorbed first precursor;

d. Purifying any unreacted nitrogen source;

e. Contacting the heated precursor with a vapor generated from a second precursor different from the first precursor to chemically adsorb a second precursor on the heated substrate;

f. purging any unadsorbed second precursor;

g. Introducing a nitrogen source onto the heated substrate to react with the adsorbed second precursor; And

h. Purging any unadsorbed nitrogen source;

Steps a to h provide a method of depositing a silicon-containing film that is repeated until a desired thickness is reached.

In another embodiment, a method is disclosed for depositing a silicon-containing film in a fluid chemical vapor deposition process wherein the substrate has at least one surface feature. As used herein, the term "surface feature" refers to a feature, such as, but not limited to, pores, trenches, wells, steps, gaps, vias, it means.

In one particular embodiment, the flowable chemical vapor deposition process comprises

내지 약 400

범위의 온도에서 유지되는 반응기에 표면 피쳐를 지닌 기판을 배치하는 단계; -20

To about 400

Disposing a substrate having surface features in a reactor maintained at a temperature in the range;

Introducing at least one precursor and a nitrogen source comprising a bisaminoalkoxysilane compound having the formula (I) in the reactor, wherein at least one compound reacts with a nitrogen source to form a nitrate containing Forming a film:

R ¹ Si (NR ² R ³ ) (NR ⁴ R ⁵ ) OR ⁶ (I)

Wherein R ¹ is a hydrogen atom, a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ alkynyl group, A C ₄ to C ₁₀ aromatic hydrocarbon group; Each of R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom, a C ₄ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ An alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; R ⁶ is a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₂ to C ₁₀ alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; Optionally in formula (I), R ² and R ³ , R ⁴ and R ⁵ , or both, may be joined together to form a ring; Optionally R < ² > and R < ⁴ > in the formula (I) may be joined together to form a diamino group; And

내지 약 1000

범위의 하나 이상의 온도에서 산소 공급원으로 처리하여 표면 피쳐의 적어도 일부 상에 필름을 형성시키는 단계를 포함한다. 대안의 구체예에서, 필름은 약 100

내지 약 1000

범위의 온도에서 UV 조사에 노출되는 동안 산소 공급원에 노출된다. 공정 단계들은 표면 피쳐가 고품질의 실리콘 옥사이드 필름으로 채워질 때까지 반복될 수 있다. The substrate was baked at about 100

To about 1000

Lt; RTI ID = 0.0 > 1 < / RTI > of the surface to form a film on at least a portion of the surface feature. In an alternate embodiment, the film is about 100 < RTI ID = 0.0 >

To about 1000

Lt; RTI ID = 0.0 > UV < / RTI > The process steps can be repeated until the surface feature is filled with a high quality silicon oxide film.

In further embodiments of the methods described herein, the film is deposited using a flowable CVD process. In this embodiment,

내지 약 400

범위의 온도에서 가열되고, 100 Torr 또는 그 미만의 압력에서 유지되는 반응기에 배치하고;One or more substrates comprising surface features are treated with -20

To about 400

Lt; RTI ID = 0.0 > 100 Torr < / RTI > or less;

Introducing at least one precursor comprising a bisaminoalkoxysilane compound having the formula (I)

R ¹ Si (NR ² R ³ ) (NR ⁴ R ⁵ ) OR ⁶ (I)

Wherein R ¹ is a hydrogen atom, a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ alkynyl group, A C ₄ to C ₁₀ aromatic hydrocarbon group; Each of R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom, a C ₄ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ An alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; R ⁶ is a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₂ to C ₁₀ alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; Optionally in formula (I), R ² and R ³ , R ⁴ and R ⁵ , or both, may be joined together to form a ring; Optionally R < ² > and R < ⁴ > in the formula (I) may be joined together to form a diamino group;

Supplying an oxygen source to the reactor to react with at least one compound to form a film and coat at least a portion of the surface feature;

내지 약 1000

범위의 하나 이상의 온도에서 어닐링하여 실리콘-함유 필름이 표면 피쳐의 적어도 일부를 피복시키는 것을 포함한다. 상기 구체예의 산소 공급원은 수증기, 물 플라즈마, 오존, 산소, 산소 플라즈마, 산소/헬륨 플라즈마, 산소/아르곤 플라즈마, 질소 옥사이드 플라즈마, 이산화탄소 플라즈마, 과산화수소, 유기 퍼옥사이드, 및 이들의 혼합물로 이루어진 군으로부터 선택된다. 공정은 표면 피쳐가 실리콘-함유 필름으로 채워질 때까지 반복될 수 있다. 수증기가 이러한 구체예에서 산소 공급원으로서 사용되는 경우, 기판 온도는 바람직하게는 -20 내지 100

, 매우 바람직하게는 -10 내지 80

이다.The film was coated at about 100

To about 1000

Lt; RTI ID = 0.0 > silicon-containing < / RTI > film to cover at least a portion of the surface feature. The oxygen source of the embodiments is selected from the group consisting of water vapor, water plasma, ozone, oxygen, oxygen plasma, oxygen / helium plasma, oxygen / argon plasma, nitrogen oxide plasma, carbon dioxide plasma, hydrogen peroxide, organic peroxide, do. The process can be repeated until the surface features are filled with the silicon-containing film. When water vapor is used as the oxygen source in these embodiments, the substrate temperature is preferably between -20 and 100

, Very preferably -10 to 80

to be.

In one particular embodiment, a method for depositing a film selected from silicon oxynitride and carbon-doped silicon oxynitride with a fluid chemical vapor deposition process comprises

내지 약 400

범위의 온도에서 유지되는 반응기에 배치하고; A substrate having a surface feature is referred to as -20

To about 400

Placing in a reactor maintained at a temperature in the range of;

Introducing into the reactor at least one precursor comprising a bisaminoalkoxysilane compound having the formula (I) and a nitrogen source, wherein at least one compound reacts with a nitrogen source to form a nitrile-containing film on at least a portion of the surface features Lt; / RTI >

R ¹ Si (NR ² R ³ ) (NR ⁴ R ⁵ ) OR ⁶ (I)

Wherein R ¹ is a hydrogen atom, a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ alkynyl group, A C ₄ to C ₁₀ aromatic hydrocarbon group; Each of R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom, a C ₄ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ An alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; R ⁶ is a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₂ to C ₁₀ alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; Optionally in formula (I), R ² and R ³ , R ⁴ and R ⁵ , or both, may be joined together to form a ring; Optionally R < ² > and R < ⁴ > in the formula (I) may be joined together to form a diamino group;

내지 약 1000

범위의 온도에서 UV 조사에 노출되어 형성되는 필름을 치밀화시킬 수 있다. And treating the substrate with a nitrogen source to form at least a portion of the surface feature by forming a silicon oxynitride or carbon-doped silicon oxynitride film. Optionally, the film may be about 100

To about 1000

It is possible to densify the film formed by exposure to UV radiation at a range of temperatures.

일 수 있다. 일 특정 구체예에서, 공정은 화학식 (I) 또는 A를 지닌 비스아미노알콕시실란로부터 생성된 증기를 가열된 기판과 접촉시켜 전구체를 가열된 기판 상에 화학적으로 흡착시키는 단계; 어떠한 흡착되지 않은 전구체를 퍼징시켜 내는 단계; 환원제를 도입하여 흡착된 전구체를 환원시키는 단계; 및 어떠한 미반응된 환원제를 퍼징시켜 내는 단계를 포함한다.In a further embodiment, the present disclosure provides a method of fabricating a silicon-on-insulator substrate using cyclic chemical vapor deposition (CCVD) or atomic layer deposition (ALD) techniques, such as, but not limited to, plasma enhanced ALD (PEALD) or plasma enhanced CCVD (PECCVD) Containing film is described. In these embodiments, the deposition temperature may be relatively high to control the details of the film properties required in a particular semiconductor application,

Lt; / RTI > In one particular embodiment, the process comprises the steps of chemically adsorbing a precursor on a heated substrate by contacting a vapor produced from a bisaminoalkoxysilane having the formula (I) or A with a heated substrate; Purging any unadsorbed precursor; Introducing a reducing agent to reduce the adsorbed precursor; And purifying any unreacted reducing agent.

In another embodiment, a container for depositing a silicon-containing film comprising at least one bisaminoalkoxysilane precursor compound having the formula (I) is described herein. In one particular embodiment, the vessel comprises at least one pressurizable vessel (preferably made of stainless steel) equipped with suitable valves and fittings to deliver one or more precursors to a reactor for CVD or ALD processing. In these or other embodiments, the bisaminoalkoxysilane precursor is provided in a pressurizable container of stainless steel, and the purity of the precursor is 98 wt% or greater or 99.5 wt% or greater, which is suitable for most semiconductor applications . In certain embodiments, such a container may also have means for mixing the precursor with one or more additional precursors as desired. In these or other embodiments, the contents of the container (s) may be premixed with further precursors. Alternatively, the bisaminoalkoxysilane precursor and / or other precursor may be maintained in a separate vessel, or in a single vessel with separate means for maintaining the bisaminoalkoxysilane precursor and the other precursor separately during storage.

In one embodiment of the process described herein, a cyclic deposition process such as CCVD, ALD, or PEALD can be used, wherein at least one bisaminoalkoxysilane precursor having the formula (I) and optionally a nitrogen- For example, a plasma containing ammonia, hydrazine, monoalkyl hydrazine, dialkyl hydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen and hydrogen is used.

Throughout the specification, the term "ALD or ALD-like" refers to a process including, but not limited to, a) reacting each reactant comprising a bisaminoalkoxysilane precursor and a reactive gas in a reactor such as a single wafer ALD Are sequentially introduced into a reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor; b) each reactant comprising a bisaminoalkoxysilane precursor and a reactive gas is exposed to the substrate by moving to or rotating relative to the substrate in a different section of the reactor, each section comprising an inert gas curtain, Space ALD reactor, or a roll-to-roll ALD reactor.

In certain embodiments, the silicon-containing film is deposited using a fluid chemical vapor deposition (FCVD) process. In one particular embodiment of the FCVD process, the bisaminoalkoxysilane precursor described herein is reacted with a protic reagent, such as water, to form a flowable liquid that can fill at least a portion of the surface features of the substrate, optionally with thermal annealing wherein the substrate is treated with at least one process selected from the group consisting of annealing, annealing, ultraviolet (UV) light exposure, and infrared (IR) to provide solid silicon and an oxygen containing film. In another embodiment of the FCVD process, the bisaminoalkoxysilane precursor described herein is reacted with an oxygen source (other than water) to form a flowable liquid that can fill at least a portion of the surface features of the substrate, optionally followed by thermal annealing, ultraviolet (UV) light exposure, and infrared (IR) to provide a solid silicon and oxygen containing film. In still further embodiments described herein, the bisaminoalkoxysilane precursors described herein form a flowable liquid that can react with the nitrogen source to fill at least a portion of the surface features of the substrate and can be thermally annealed, ultraviolet (UV) Treating the substrate with at least one process selected from the group consisting of light exposure, infrared light (IR) to provide a solid silicon and nitrogen containing film, optionally treating the solid silicon and nitrogen containing film with an oxygen source, Containing film. The nitrogen-containing source may be a plasma comprising ammonia, hydrazine, monoalkyl hydrazine, dialkyl hydrazine, nitrogen and hydrogen, ammonia plasma, nitrogen plasma, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, Tertiary-butylamine, ethylenediamine, ethanolamine, but not limited to, organic amines, organic amine plasmas. In yet another embodiment of the FCVD process, the bisaminoalkoxysilane precursor described herein forms a flowable liquid that can react with a plasma source to fill at least a portion of the surface features of the substrate and optionally perform thermal annealing, ultraviolet (UV) Light exposure, and infrared (IR), to provide a solid silicon-containing film. The plasma source may be selected from the group consisting of a helium plasma, an argon plasma, a plasma comprising helium and hydrogen, a plasma comprising argon and hydrogen. When the plasma is applied to FCVD or other deposition processes, the plasma may be generated in situ or remotely. With respect to embodiments employing FCVD deposition processes, in one particular embodiment the remote plasma generator is used because it makes the structure on the substrate less subject to damage.

As noted above, the methods described herein can be used to deposit a silicon-containing film on at least a portion of a substrate. Examples of suitable substrates include, but are not limited to, silicon, SiO _2, Si ₃ N _4, OSG, FSG, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonyl Such as, but not limited to, TiN, Ti (C) N, TiN, TiN, and the like, as well as other materials such as, for example, nitrides, boronitrides, antireflective coatings, photoresists, organic polymers, porous organic and inorganic materials, metals such as copper and aluminum, , TaN, Ta (C) N, Ta, W, or WN. The film is compatible with several subsequent processing steps such as, for example, chemical mechanical planarization (CMP) and anisotropic etching processes.

The deposited film may include a computer chip, an optical element, a magnetic information storage, a coating on a support material or substrate, a microelectromechanical system (MEMS), a nanoelectromechanical system, a thin film transistor (TFF), and a liquid crystal display (LCD) But are not limited to these.

Example

Example 1: Synthesis of bis (tert-butylamino) ethoxymethylsilane

로 냉각된 1.5L의 무수 THF 중의 72.0g (481.7mmol)의 메틸트리클로로실란의 용액에 반응의 내부 온도를 -30

로 유지하면서 추가의 깔때기를 통해 140.9g (1926.7mmol)의 3차-부틸아민을 적가하였다. 형성된 백색 슬러리를 기계식 교반기로 교반하였다. 3차-부틸아민 하이드로클로라이드 염을 형성된 진한 슬러리로부터 여과해 내고, 추가의 200mL의 헥산으로 세척하고, 가압하여 염 안에 포집될 가능성이 있는 잔류 생성물을 축출하였다. 별도의 반응에서, -30

에서의 300mL의 무수 THF 중의 22.2g (480.8mmol) 에탄올의 용액에, 내부 온도를 -30

로 유지하면서 헥산 중의 205.0mL (512.5mmol)의 2.5M n-부틸리튬 용액을 적가하였다. nBuLi의 첨가가 완료된 후, 반응 혼합물은 등명한 색에서 밝은 황색 현탁액으로 변하였다. 이후, 반응 혼합물을 실온으로 가온되게 하고, 자기 교반 막대로 교반하였다. 밤새 교반한 후, 리튬 에톡사이드 반응 혼합물은 밝은 황색 현탁액에서 백색 슬러리로 변하였다. 이후, 리튬 에톡사이드 반응물을 <0

에서 반응을 유지하면서, 단계 1로부터의 여과된 반응 혼합물에 부가 깔때기를 통해 인시튜로 첨가하였다. 리튬 에톡사이드의 첨가는 반응이 그러한 발열반응이지 않음이 목격됨에 따라 다소 빠르게 이루어졌다. 형성된 백색 현탁액을 실온으로 가온되게 하고 교반하였다. 수시간의 경과 후, 반응 혼합물은 백색 현탁액에서 황색으로, 오렌지색으로 변하였다. 미정제 반응 혼합물을 중간 프릿을 통해 여과하여 염화리튬을 연상시키는 25.0g의 갈색 고형물을 형성시켰다. 여액은 호박 오렌지색 용액이었고, 용매를 제거하기 위해 50

의 오일조 온도로 100Torr에서 회전증발 처리하였다. 109.26g의 미정제 물질의 분리 및 정제를 82

및 10Torr에서 분별 증류에 의해 수행하였다. 51.4g의 등명한 액체가 92.5% 검정에서 분리되었다. 열중량 분석(Thermogravimetric analysis) (TGA)/ 시차 주사 열량법(differential scanning calorimetry) (DCS)은 205

에서의 비점 및 2.52% 잔여물을 나타냈다. 안정성 시험은 80

에서 4일 동안 가열 후 0.38%의 평균 순도 증가를 나타냈다. 분석은 90.18%에서 90.56%로 증가한 것으로 나타났다. -30

To a solution of 72.0 g (481.7 mmol) of methyltrichlorosilane in 1.5 L of anhydrous THF cooled to -30

140.9 g (1926.7 mmol) of tert-butylamine was added dropwise through an additional funnel while maintaining the temperature at < RTI ID = 0.0 &gt; The resulting white slurry was stirred with a mechanical stirrer. The tert-butylamine hydrochloride salt was filtered from the thick slurry formed, washed with an additional 200 mL of hexane, and pressurized to remove any residual product that could be trapped in the salt. In a separate reaction, -30

To a solution of 22.2 g (480.8 mmol) ethanol in 300 mL dry THF at -30

(512.5 mmol) of a 2.5M solution of n-butyllithium in hexane was added dropwise. After the addition of nBuLi was complete, the reaction mixture turned from a light color to a light yellow suspension. The reaction mixture was then allowed to warm to room temperature and stirred with a magnetic stir bar. After stirring overnight, the lithium ethoxide reaction mixture turned from a light yellow suspension to a white slurry. Thereafter, the lithium ethoxide reactant was allowed to react at &lt; 0

Was added in-situ via an addition funnel to the filtered reaction mixture from step 1, maintaining the reaction at &lt; RTI ID = 0.0 &gt; The addition of lithium ethoxide was somewhat faster as the reaction was observed to be not such an exothermic reaction. The resulting white suspension was allowed to warm to room temperature and stirred. After several hours, the reaction mixture turned from a white suspension to yellow and orange. The crude reaction mixture was filtered through an intermediate frit to form 25.0 g of brown solids reminiscent of lithium chloride. The filtrate was an orange pumpkin solution and 50 &lt; RTI ID = 0.0 &gt;

At 100 Torr with the oil bath temperature of &lt; RTI ID = 0.0 &gt; Separation and purification of 109.26 g of crude material was carried out as described in 82

And fractional distillation at 10 Torr. 51.4 g of clarified liquid was separated in 92.5% assay. Thermogravimetric analysis (TGA) / differential scanning calorimetry (DCS)

Lt; / RTI &gt; and a 2.52% residue. The stability test was 80

Showed an average purity increase of 0.38% after heating for 4 days. The analysis showed an increase from 90.18% to 90.56%.

Example 2: Synthesis of bis (tert-butylamino) methoxymethylsilane

로 냉각된 1.5L의 무수 THF 중의 72.0g (481.7mmol)의 메틸트리클로로실란의 용액에 반응의 내부 온도를 -30

로 유지하면서 추가의 깔때기를 통해 140.9g (1926.7mmol)의 3차-부틸아민을 적가하였다. 형성된 백색 슬러리를 기계식 교반기로 교반하였다. 3차-부틸아민 하이드로클로라이드 염을 형성된 진한 슬러리로부터 여과해 내고, 추가의 200mL의 헥산으로 세척하고, 가압하여 염 안에 포집될 가능성이 있는 잔류 생성물을 축출하였다. 별도의 반응에서, -30

에서의 300mL의 무수 THF 중의 15.4 g (481.7mmol) 메탄올의 용액에, 내부 온도를 -30

로 유지하면서 헥산 중의 202.3mL (505.8mmol)의 2.5M n-부틸리튬 용액을 적가하였다. nBuLi의 첨가가 완료된 후, 반응 혼합물을 실온으로 가온되게 하고, 자기 교반 막대로 교반하였다. 밤새 교반한 후, 리튬 메톡사이드 반응 혼합물을 <0

에서 반응을 유지하면서, 단계 1로부터의 여과된 반응 혼합물에 부가 깔때기를 통해 인시튜로 첨가하였다. 형성된 백색 현탁액을 실온으로 가온되게 하고 교반하였다. 총 250mL의 THF를 첨가하여 반응이 완료되게 하기 위한 충분한 용해도를 제공하였다. 여과에 의해 염화리튬을 연상시키는 21.5g으로 칭량되는 약간 황색의 분말을 얻었다. 여액으로부터 회전증발에 의해 용매를 제거하여 122.45g의 미정제 물질을 분리시켰다. 정제를 75 및 10Torr에서 패킹된 컬럼(packed column)을 사용하여 진공 증류에 의해 수행하였다. 78.7g의 양으로 등명한 액체가 분리되었다. 샘플을 안정성 및 TGA/DCS에 대해 처리하였다. DSC는 186.6

의 비점을 나타냈다. 추가 관측은 80

에서 3일 동안 3회 가열 후 0.08%의 평균 증가(90.79%에서 90.87%로)를 나타냈다. -30

To a solution of 72.0 g (481.7 mmol) of methyltrichlorosilane in 1.5 L of anhydrous THF cooled to -30

140.9 g (1926.7 mmol) of tert-butylamine was added dropwise through an additional funnel while maintaining the temperature at < RTI ID = 0.0 &gt; The resulting white slurry was stirred with a mechanical stirrer. The tert-butylamine hydrochloride salt was filtered from the thick slurry formed, washed with an additional 200 mL of hexane, and pressurized to remove any residual product that could be trapped in the salt. In a separate reaction, -30

To a solution of 15.4 g (481.7 mmol) methanol in 300 mL dry THF at -30

(505.8 mmol) of a 2.5M solution of n-butyllithium in hexane was added dropwise. After the addition of nBuLi was complete, the reaction mixture was allowed to warm to room temperature and stirred with a magnetic stir bar. After stirring overnight, the lithium methoxide reaction mixture was &lt; 0

Was added in-situ via an addition funnel to the filtered reaction mixture from step 1, maintaining the reaction at &lt; RTI ID = 0.0 &gt; The resulting white suspension was allowed to warm to room temperature and stirred. A total of 250 mL of THF was added to provide sufficient solubility to complete the reaction. A slightly yellow powder was obtained which was weighed to 21.5 g which was reminiscent of lithium chloride by filtration. The solvent was removed by rotary evaporation from the filtrate to isolate 122.45 g of crude material. Tablets 75 &Lt; / RTI &gt; and a packed column at 10 Torr. A clear liquid was separated in an amount of 78.7 g. Samples were processed for stability and TGA / DCS. DSC 186.6

Respectively. Additional observations are 80

Showed an average increase of 0.08% (from 90.79% to 90.87%) after 3 times of heating for 3 days.

Example 3: Synthesis of bis (tert-butylamino) isopropoxymethylsilane

로 냉각된 50mL의 헥산 중의 3.35g (22.44mmol)의 메틸트리클로로실란의 용액에 반응의 내부 온도를 -30

로 유지하면서 6.56g (89.75 mmol)의 3차-부틸아민을 적가하였다. 형성된 백색 슬러리를 자기 교반 막대로 교반하였다. 백색 염으로서 3차-부틸아민 하이드로클로라이드를 형성된 진한 슬러리로부터 여과해 내고, 추가의 20mL의 헥산으로 세척하고, 가압하여 염 안에 포집될 가능성이 있는 잔류 생성물을 축출하였다. 별도의 반응에서, -30

에서의 30mL의 무수 THF 중의 1.35 g (22.44mmol) 이소프로필 알코올의 용액에, 내부 온도를 -30

로 유지하면서 헥산 중의 9.0mL (22.4mmol)의 2.5M n-부틸리튬 용액을 적가하였다. nBuLi의 첨가가 완료된 후, 반응 혼합물을 실온으로 가온되게 하고, 단계 1로부터의 여과된 반응 혼합물에 인시튜로 첨가하였다. 형성된 백색 현탁액을 밤새 교반한 후, 이를 중간 프릿을 통해 여과하여 LiCl을 연상시키는 백색 고형물을 분리시켰다. 여액은 오렌지색-황색 용액이었다. 증류를 240Torr 및 50

에서 수행하여 용매를 제거하였다. 용매를 제거하자, 보다 많은 LiCl 염이 침전하였고, 0.24g의 양으로 분리되었다. 벌브 투 벌브 진공 트랜스퍼(bulb to bulb vacuum transfer)를 <1Torr 및 90

에서 수행하여 2.67g의 등명한 액체를 분리시켰다. 정제된 물질의 GC/GC-MS를 실행하였다. TGA/DCS는 212.5

에서의 비점 및 0.70% 잔여물을 나타냈다. 3일 동안 80

로의 가열에 의해 수행된 안정성 시험은 평균 순도가 90.17%에서 90.12%로 감소하였음을 나타냈다. -30

To a solution of 3.35 g (22.44 mmol) of methyltrichlorosilane in 50 mL of hexane cooled to -30

6.56 g (89.75 mmol) of tert-butylamine was added dropwise. The resulting white slurry was stirred with a magnetic stir bar. Tert-Butylamine hydrochloride as a white salt was filtered from the thick slurry formed, washed with an additional 20 mL of hexane, and pressurized to remove any residual product that could be trapped in the salt. In a separate reaction, -30

To a solution of 1.35 g (22.44 mmol) isopropyl alcohol in 30 mL dry THF at -30

(22.4 mmol) of a 2.5 M solution of n-butyllithium in hexane was added dropwise. After the addition of nBuLi was complete, the reaction mixture was allowed to warm to room temperature and was added in-situ to the filtered reaction mixture from step 1. The resulting white suspension was stirred overnight, which was then filtered through an intermediate frit to isolate a white solid reminiscent of LiCl. The filtrate was orange-yellow solution. Distillation at 240 Torr and 50

To remove the solvent. Upon removal of the solvent, more LiCl salt precipitated and separated in an amount of 0.24 g. Bulb to bulb vacuum transfer to <1 Torr and 90

To isolate 2.67 g of the clear liquid. GC / GC-MS of the purified material was run. TGA / DCS is 212.5

Lt; / RTI &gt; and a 0.70% residue. 80 days for 3 days

Showed that the average purity decreased from 90.17% to 90.12%. &Lt; tb &gt;&lt; TABLE &gt;

Example 4: Synthesis of bis (isopropylamino) tert-butoxymethylsilane

0.34 g (4.6 mmol) of anhydrous tert-butanol was added to 1.0 g (4.6 mmol) of tris (isopropylamino) methylsilane in 20 mL of hexane. Over a month, gas chromatography mass spectrometry (GC-MS) demonstrated the desired product with a parent peak of 233 amu. The stability of the compounds was not determined.

Comparative Example 1: Synthesis of bis (isopropylamino) ethoxymethylsilane

0.21 g (4.6 mmol) of anhydrous ethanol was added to 1.0 g (4.6 mmol) of tris (isopropylamino) methylsilane in 20 mL of hexane. GC-MS showed the desired product with a parent peak of 204 amu. After several days GC-MS and gas chromatography (GC) were performed on the reaction mixture and two new peaks were expressed since the last analysis. The GC / GC-MS showed that the mixture had two (2) doubtful peaks with a parent peak of 148 amu (in order of increasing residence time), four (4) MTES, one (1) isopropylamino-bis-ethoxymethylsilane with a parent peak of 191 amu , 2 parts of the desired product, and 10 parts of tris (isopropylamino) methylsilane. This indicates that a ligand change is taking place and the compound is not stable. By comparison, the compounds in Examples 1-3 with tert-butylamino groups would be more stable and better precursors.

Comparative Example 2: Synthesis of bis (isopropylamino) isopropoxymethylsilane (comparative example)

에서 40.27g (670mmol)의 무수 이소프로필 알코올을 첨가하였다. 한 달의 기간 후, GC/GC-MS는 13 대 6 대 43 대 31의 트리스-이소프로폭시 대 비스-이소프로폭시 대 치환된 하나의 이소프로폭시 대 트리스(이소프로필아미노)메틸실란의 비를 나타냈다. 비교 실시예 1과 같이, 이는 리간드 변화가 일어나고 있고, 화합물이 안정하지 않음을 나타낸다.To 145.67 g (670 mmol) of tris (isopropylamino) methylsilane in 1.0 L of hexane was added -20

Was added 40.27 g (670 mmol) of anhydrous isopropyl alcohol. After one month period, the GC / GC-MS showed a ratio of 13 to 6 versus 43 to 31 of tris-isopropoxy versus bis-isopropoxy versus one isopropoxy to tris (isopropylamino) methylsilane substituted Respectively. As in Comparative Example 1, this indicates that a ligand change is taking place and the compound is not stable.

Example 5: Hydrolysis of bis (tert-butylamino) ethoxymethylsilane in the presence of iso-propyl alcohol

The compound bis (tert-butylamino) ethoxymethylsilane was prepared as shown in Example 1. One part by volume of bis (tert-butylamino) ethoxymethylsilane was mixed with 10 parts of a 20% aqueous solution in isopropyl alcohol. The mixture was monitored by GC at 1 hour after the initial mixing and showed complete hydrolysis / condensation of bis-tert-butylaminoethoxymethylsilane but no gelation. The mixture eventually geled within 16 hours, indicating that it would be stable in the FCVD process due to its hydrolysis / condensation, followed by the rate of gelation. Gelling resulted in sufficient cross-linking to convert the free-flowing liquid to a solid, indicating an important feature for the FCVD precursor.

Example 6: Comparison between bis (tert-butylamino) ethoxymethylsilane spin-coated film and tris-isopropylaminomethylsilane film after aging

에서 열처리하고, 푸리에 변환 적외선 분광법(Fourier Transform Infrared Spectroscopy)(FTIR)에 의해 분석하였다. 필름은 트리스-이소프로필아미노메틸실란 필름의 것과 유사한 Si-OH 결합이 증착되지 않음을 나타내었다. 비교용 트리스-이소프로필아미노메틸실란 필름을 하기와 같이 제조하였다: 1 부피부의 트리스-이소프로필아미노메틸실란을 5 부의 이소프로필 알코올 중의 20% 수용액과 혼합하였다. 혼합물을 주위 조건 하에서 1시간 동안 에이징시킨 후, 2000 rpm에서 Laurell WS-400 스핀 코터를 사용하여 실리콘 웨이퍼 상에서 스피닝시켰다. 트리스-이소프로필아미노메틸실란 필름이 그것의 보다 빠른 가수분해/축합 속도로 인해 비스(3차-부틸아미노)에톡시메틸실란 필름보다 더 짧은 시간 동안에 에이징되었다. 웨이퍼를 10분 동안 150

에서 열처리하고, FTIR에 의해 분석하였으며, Si-OH가 증착되지 않음을 나타내었고, 이는 필름이 완전히 가교됨을 나타낸다. 비교 용도는 어떠한 필름도 Si-OH 결합을 갖지 않음을 나타내었다. Compound bis (tert-butylamino) ethoxymethylsilane was prepared as shown in Example 1. (Tert-butylamino) ethoxymethylsilane was mixed with a 20% aqueous solution in 4 parts of isopropyl alcohol, aged for 2 hours under ambient conditions, and then transferred to a Laurell WS-400 spin coater at 2000 rpm coater on a silicon wafer. The wafer was immersed in 150 &lt; RTI ID =

, And analyzed by Fourier Transform Infrared Spectroscopy (FTIR). The films showed that Si-OH bonds similar to those of the tris-isopropylaminomethylsilane film were not deposited. A comparative tris-isopropylaminomethylsilane film was prepared as follows: Part 1 skin tris-isopropylaminomethylsilane was mixed with 5 parts of 20% aqueous solution in isopropyl alcohol. The mixture was aged under ambient conditions for 1 hour and then spun on a silicon wafer using a Laurell WS-400 spin coater at 2000 rpm. The tris-isopropylaminomethylsilane film was aged for a shorter time than the bis (tert-butylamino) ethoxymethylsilane film due to its faster hydrolysis / condensation rate. The wafer was immersed in 150 &lt; RTI ID =

And analyzed by FTIR, indicating that Si-OH was not deposited, indicating that the film was completely crosslinked. The comparison shows that no film has Si-OH bonds.

Example 7: Hydrolysis of bis (tert-butylamino) ethoxymethylsilane in the presence of iso-propyl alcohol and Surfynol® 61 (3,5-dimethyl-1-hexyn-

Compound bis (tert-butylamino) ethoxymethylsilane was prepared as shown in Example 1. Bis (tert-butylamino) ethoxymethylsilane was mixed with 4 parts of a 20% aqueous solution in a 1: 4 mixture of Surfynol 61 versus isopropyl alcohol. The mixture was aged under ambient conditions for 2 hours and then spun on a silicon wafer using a Laurell WS-400 spin coater at 2000 rpm. Similarly, one part by volume of bis-tert-butylaminoethoxymethylsilane was mixed with 4 parts of a 20% aqueous solution in a 1: 4 mixture of Surfynol (R) 61 to isopropyl alcohol and aged for 2 hours, Lt; / RTI &gt; The addition of Surfynol® 61 did not improve the uniformity of the spinning film.

Example 8: Hydrolysis of bis (tert-butylamino) ethoxymethylsilane in the presence of ethanol

Compound bis (tert-butylamino) ethoxymethylsilane was prepared as shown in Example 1. Bis (tert-butylamino) ethoxymethylsilane in one part skin was mixed with 10 parts of a 20% aqueous solution in ethanol. The mixture was monitored by GC one hour after the initial mixing and showed complete hydrolysis / condensation of bis-tert-butylaminoethoxymethylsilane, but no gelation occurred. The mixture eventually geled within 16 hours, indicating that it would be suitable for the FCVD process due to its hydrolysis / condensation, followed by the rate of gelation.

Example 9: Hydrolysis of bis (tert-butylamino) ethoxymethylsilane in the presence of ethanol

Compound bis (tert-butylamino) ethoxymethylsilane was prepared as shown in Example 1. One part skin of bis (tert-butylamino) ethoxymethylsilane was mixed with 4 parts of a 20% aqueous solution in ethanol. The mixture was monitored by GC one hour after the initial mixing and showed complete hydrolysis / condensation of bis-tert-butylaminoethoxymethylsilane, but no gelation occurred. The mixture eventually geled within 16 hours, indicating that it would be suitable for the FCVD process due to its hydrolysis / condensation, followed by the rate of gelation.

Example 10: Synthesis of bis (tert-butylamino) ethoxymethylsilane in the presence of ethanol

Compound bis (tert-butylamino) ethoxymethylsilane was prepared as shown in Example 1. One part skin of bis-tert-butylaminoethoxymethylsilane was mixed with 4 parts of a 20% aqueous solution in ethyl alcohol. The mixture was aged under ambient conditions for 2 hours and then spun on a silicon wafer using a Laurell WS-400 spin coater at 2000 rpm. The formed film was a white powder and was not uniform. This example shows that the addition of alcohol provides different physical characteristics of the spinning film.

Example 11: Hydrolysis of bis (tert-butylamino) methoxymethylsilane in the presence of iso-propyl alcohol

Compound bis (tert-butylamino) ethoxymethylsilane was prepared as shown in Example 2. One part skin of bis-tert-butylaminomethoxymethylsilane was mixed with 10 parts of a 20% aqueous solution in isopropyl alcohol. The mixture was monitored by GC for one hour after the initial mixing and showed complete hydrolysis / condensation of bis-tert-butylaminomethoxymethylsilane, but no gelation occurred. The mixture eventually geled within 16 hours, indicating that its hydrolysis / condensation, followed by the rate of gelation, would be suitable in the FCVD process.

Example 12: Hydrolysis of bis (tert-butylamino) methoxymethylsilane in the presence of iso-propyl alcohol

Compound bis (tert-butylamino) ethoxymethylsilane was prepared as shown in Example 2. One part skin of bis-tert-butylaminomethoxymethylsilane was mixed with 4 parts of 20% aqueous solution in isopropyl alcohol. The mixture was monitored by GC and the hydrolysis / condensation degree of the precursor was measured at 5 minutes, 30 minutes, and 2 hours after the initial mixing, indicating that a significant amount of bis-tert-butylaminomethoxymethylsilane was hydrolyzed / Condensation occurred but gelation did not occur. The mixture eventually geled within 16 hours, indicating that it would be suitable for the FCVD process due to its hydrolysis / condensation, followed by the rate of gelation.

Example 13: Deposition of a flowable carbon-doped silicon oxynitride film using bis (tert-butylamino) methoxymethylsilane

cm)의 단결정 실리콘 웨이퍼 기판 상 및 실리콘 패턴 웨이퍼 상에 증착시켰다. 특정 예에서, 기판은 사전-증착 처리, 예컨대, 비제한적으로, 플라즈마 처리, 열처리, 화학 처리, 자외선광 노출, 전자빔 노출 및/또는 필름의 하나 이상의 성질에 영향을 미치는 그 밖의 처리에 노출될 수 있다. The flowable CVD film was immersed in a medium resistance (8-12

cm &lt; / RTI &gt; monocrystalline silicon wafer substrate and on a silicon pattern wafer. In certain instances, the substrate may be exposed to a pre-deposition treatment such as, but not limited to, plasma treatment, heat treatment, chemical treatment, ultraviolet light exposure, electron beam exposure and / or other treatments affecting one or more properties of the film have.

또는 300~400

의 변형된 PECVD 챔버를 사용하여 열적으로 어닐링시키고, 진공 하에 UV 경화시켰다. 632 nm에서의 두께 및 굴절률(refractive index)(RI)을 SCI 반사계(reflectometer) 또는 Woollam 타원계(ellipsometer)에 의해 측정하였다. 전형적인 필름 두께는 10 내지 2000 nm의 범위였다. 실리콘-기반 필름의 수소 함유물(Si-H, C-H 및 N-H)의 결합 특성을 측정하고, Nicolet 전송 푸리에 변환 적외선 분광법(FTIR) 기구로 측정하였다. 모든 밀도 측정은 X-선 반사율(reflectivity)(XRR)을 사용하여 달성되었다. X-선 광전자 분광학(Photoelectron Spectroscopy)(XPS) 및 2차 이온 질량 분석법(Secondary ion mass spectrometry)(SIMS) 분석을 수행하여 필름의 원소 조성을 측정하였다. 패턴화된 웨이퍼에 대한 유동성 및 갭 필(gap fill) 효과를 2.0 nm의 해상도에서 Hitachi S-4700 시스템을 사용하여 단면 주사 전자 현미경 (Cross-sectional Scanning Electron Microscopy) (SEM)에 의해 관찰하였다.Deposition was performed with a Applied Materials Precision 5000 system in a modified 200 mm DXZ chamber using a silane or TEOS process kit. The PECVD chamber was equipped with direct liquid injection (DLI) delivery capability. The precursor was a liquid having a transfer temperature based on the boiling point of the precursor. To deposit the initial fluidity nitride film, were typical liquid precursor flow rate of 100-5000 mg / min, in-situ plasma power density (power density) of 0.25 - 3.5 was a W / cm ^2, pressure of 0.75 - was 12 Torr. In order to densify the deposited flowable film,

Or 300 to 400

, &Lt; / RTI &gt; thermally annealed using a modified PECVD chamber and UV cured under vacuum. The thickness and refractive index (RI) at 632 nm were measured by an SCI reflectometer or a Woollam ellipsometer. Typical film thicknesses ranged from 10 to 2000 nm. The bonding properties of the hydrogen-containing materials (Si-H, CH and NH) of the silicon-based film were measured and measured by a Nicolet transfer Fourier transform infrared spectroscopy (FTIR) instrument. All density measurements were achieved using X-ray reflectivity (XRR). The composition of the film was measured by X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS) analysis. Flowability and gap fill effects on patterned wafers were observed by Cross-sectional Scanning Electron Microscopy (SEM) using a Hitachi S-4700 system at a resolution of 2.0 nm.

, 바람직하게는 0 내지 40

의 범위였다. DOE 실험을 사용하여 어떠한 공정 파라미터가 우수한 유동성을 지닌 최적의 필름을 생산하는지를 결정하였다.Flowable CVD deposition was performed using the design of experiment (DOE) methodology. Experimental designs include precursor flow rates of 100 to 5000 mg / min, preferably 1000 to 2000 mg / min; An NH ₃ flow rate of 100 sccm to 1000 sccm, preferably 100 to 300 sccm; Pressure 0.75 to 12 Torr, preferably 6 to 10 Torr; RF power (13.56 MHz) 100-1000 W, preferably 100-500 W; A low-frequency (LF) power of 0 to 100 W; The deposition temperature ranges from 0 to 550

, Preferably 0 to 40

Respectively. DOE experiments were used to determine which process parameters produced the best film with good flowability.

. 블랭킷 Si 웨이퍼 상에, 습윤되고 점착성인 SiCON 필름을, 열적 어닐링 및 UV 경화 후 10% 내지 50% 범위의 수축률로 증착시켰다. 단면 주사 전자 현미경(SEM) 이미지의 검토에 의해 유동성 CVD 공정에서 비스(3차-부틸아미노)메톡시메틸실란을 사용함으로써 상향식(bottom-up)의, 이음매가 없고, 기공이 없는 갭-필링이 패턴 웨이퍼, 또는 적어도 하나의 표면 피쳐를 지닌 웨이퍼에 대해 달성되었음이 나타났다. In one experiment, the process conditions used to provide the most optimal film properties were: Bis (tert-butylamino) methoxymethylsilane flow rate = 1000 mg / min, NH ₃ flow rate = 0 to 450 sccm, He = 100 sccm, pressure = 8 torr, power = 300 to 600 W, and temperature = 30 to 40

. On the blanket Si wafer, a wet and tacky SiCON film was deposited with a shrinkage in the range of 10% to 50% after thermal annealing and UV curing. Bottom-up, seamless, pore-free gap-filling by using bis (tertiary-butylamino) methoxymethylsilane in a fluid CVD process by reviewing a cross-sectional scanning electron microscope (SEM) Pattern wafers, or wafers with at least one surface feature.

Claims (12)

A bisaminoalkoxysilane compound having the formula (I)
R ¹ Si (NR ² R ³ ) (NR ⁴ R ⁵ ) OR ⁶ (I)
In this formula,
R ¹ is a hydrogen atom, C ₁ to C ₁₀ linear alkyl, C ₃ to C ₁₀ branched alkyl, C ₃ to C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ alkenyl groups, C ₃ to C ₁₀ alkynyl group, C ₄ to is selected from C ₁₀ aromatic hydrocarbon group; Each of R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom, a C ₄ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ An alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; R ⁶ is a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₂ to C ₁₀ alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; Optionally in formula (I), R ² and R ³ , R ⁴ and R ⁵ , or both, may be joined together to form a ring; Optionally, in formula (I), R ² and R ⁴ may be bonded together to form a diamino group. The compound according to claim 1, wherein R ¹ is a methyl group; R ² and R ⁴ are each a hydrogen atom; R ³ and R ⁵ are each a C ₃ to C ₁₀ branched alkyl group selected from tert-butyl and tert-pentyl; R ⁶ is selected from C ₁ to C ₃ linear alkyl groups and C ₃ to C ₅ branched alkyl groups. The composition of claim 1 wherein the compound is selected from the group consisting of bis (tert-butylamino) methoxymethylsilane, bis (tert-butylamino) ethoxymethylsilane, bis (tert- butylamino) isopropoxymethylsilane, bis Bis (cis-2,6-dimethylpiperidino) methoxymethylsilane, and bis (cis-2,6-dimethylpiperidino) ethoxymethylsilane. A method of forming a silicon-containing film on at least one surface of a substrate,
Providing a substrate to the reactor;
A method comprising forming a silicon-containing film on at least one surface by a deposition process using at least one precursor comprising a bisaminoalkoxysilane having the formula (I)
R ¹ Si (NR ² R ³ ) (NR ⁴ R ⁵ ) OR ⁶ (I)
In this formula,
R ¹ is a hydrogen atom, C ₁ to C ₁₀ linear alkyl, C ₃ to C ₁₀ branched alkyl, C ₃ to C ₁₀ cyclic alkyl groups, C ₃ to C ₁₀ alkenyl groups, C ₃ to C ₁₀ alkynyl group, C ₄ to is selected from C ₁₀ aromatic hydrocarbon group; Each of R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom, a C ₄ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ An alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; R ⁶ is a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₂ to C ₁₀ alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; Optionally in formula (I), R ² and R ³ , R ⁴ and R ⁵ , or both, may be joined together to form a ring; Optionally, in formula (I), R ² and R ⁴ may be bonded together to form a diamino group. 5. The method of claim 4, wherein the deposition process is selected from the group consisting of Cyclic Chemical Vapor Deposition (CCVD), Thermochemical Vapor Deposition, Plasma Enhanced Chemical Vapor Deposition (PECVD), High Density PECVD, Photon Assisted CVD, Plasma- , Chemical assisted vapor deposition, high temperature-filament chemical vapor deposition, liquid chemical precursor CVD, low energy chemical vapor deposition (LECVD), and fluid chemical vapor deposition. 5. The method of claim 4, wherein the deposition process is selected from the group consisting of atomic layer deposition (ALD), plasma enhanced ALD (PEALD), and plasma enhanced cyclic CVD (PECCVD) processes. 6. The method of claim 5, wherein the deposition process is fluid chemical vapor deposition (FCVD). A method of depositing a silicon-containing film on at least a portion of a substrate having a surface feature with a fluid chemical vapor deposition process,
-20

To about 400

Disposing a substrate having surface features in a reactor maintained at one or more temperatures in the range;
Introducing at least one precursor and a nitrogen source comprising a bisaminoalkoxysilane compound having the formula (I) in the reactor, wherein at least one compound reacts with a nitrogen source to form a nitrate containing Forming a film:
R ¹ Si (NR ² R ³ ) (NR ⁴ R ⁵ ) OR ⁶ (I)
Wherein R ¹ is a hydrogen atom, a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ alkynyl group, A C ₄ to C ₁₀ aromatic hydrocarbon group; Each of R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom, a C ₄ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₃ to C ₁₀ An alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; R ⁶ is a C ₁ to C ₁₀ linear alkyl group, a C ₃ to C ₁₀ branched alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ alkenyl group, a C ₂ to C ₁₀ alkynyl group, and a C ₄ to C ₁₀ aromatic hydrocarbon group; Optionally in formula (I), R ² and R ³ , R ⁴ and R ⁵ , or both, may be joined together to form a ring; Optionally R &lt; ² &gt; and R &lt; ⁴ &gt; in the formula (I) may be joined together to form a diamino group;
Forming a flowable film on at least a portion of the surface feature by reacting with a bisaminoalkoxysilane compound on the substrate by introducing a source selected from an oxygen source, a nitrogen-containing source, or both; And
The flowable film was coated at about 100

To about 1000

Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt; at a temperature of at least one of the ranges, to form a solid silicon and oxygen containing film on at least a portion of the surface feature. 9. The method of claim 8 wherein the flowable film is about 100 &lt; RTI ID = 0.0 &gt;

To about 1000

Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt; 9. The method of claim 8 wherein the oxygen source is selected from the group consisting of water, oxygen plasma, ozone, and combinations thereof. 9. The method of claim 8 wherein the nitrogen-containing source is selected from the group consisting of ammonia, hydrazine, monoalkyl hydrazine, dialkyl hydrazine, organic amines, plasma comprising nitrogen and hydrogen, ammonia plasma, nitrogen plasma, and organic amine plasma Way. 9. The method of claim 8, wherein the steps can be repeated until the surface feature is substantially filled with solid silicon and oxygen containing film.